Process for preparing perfuming intermediates

Abstract

The present invention relates to the field of perfumery. More particularly, it concerns valuable new chemical intermediates for producing perfuming ingredients. Moreover, the present invention comprises also a process for producing compound of formula (I).

1 . A process for the preparation of a compound of formula (I) 
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers or a mixture thereof, and wherein m is 0 or 1; R a  is a C 1-4  alkyl group, a trimethyl silyl group, a C(═O)—R c  group, a C(═O)—OR c  group, a CH 2 (OR c ) group, a CH(OR c )CH 3  group wherein R c  is a C 1-4  alkyl group; R b  is a C 1-4  alkyl group, a C(═O)—R c  group wherein R c  is a C 1-4  alkyl group; or R a  and R b  are taken together and represent a C 2-6  alkanediyl group and X is a group of formula a), b) or c); 
       
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers, and wherein each R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7 , independently from each other, represent a hydrogen atom, a C 1-6  alkyl group or a C 2-6  alkenyl group, each optionally substituted by a hydroxy or C 1-3  alkoxy group; or two groups among R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are taken together and form C 3-8  cycloalkyl or C 5-8  cycloalkenyl group, each optionally substituted by a hydroxy, C 1-3  alkyl or C 1-3  alkoxy group, and the others groups have the same meaning as defined above; each R 8 , R 9  and R 10 , independently from each other, represent a hydrogen atom, a C 1-6  alkyl group or a C 2-6  alkenyl group, each optionally substituted by a hydroxy or C 1-3  alkoxy group; or two groups among R 8 , R 9  and R 10  are taken together and form C 3-8  cycloalkyl or C 5-8  cycloalkenyl group, each optionally substituted by a hydroxy, C 1-3  alkyl or C 1-3  alkoxy group, and the other group has the same meaning as defined above; n is 0 or 1 and Y is a —CH═CR 11 —, —CHR 12 —CHR 11 — or —CH 2 —C(OH)R 11 — group wherein R 11  is a hydrogen atom or a methyl or ethyl group and R 12  is a hydroxy or a acetate group; 
         provided that m is 1 when X is a group of formula b); 
       
       comprising a cross metathesis step, in the presence of a metathesis catalyst, between compound of the formula (IIa), (IIb) or (IIc): 
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers, and wherein each R, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , n and Y have the same meaning as defined above 
         with compound of formula (III); 
       
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers or a mixture thereof, and wherein m is 0 or 1 when the cross metathesis step is performed with compound of the formula (IIa) or (IIc) or m is 1 when the cross metathesis step is performed with compound of the formula (IIb), R a  is a C 1-4  alkyl group, a trimethyl silyl group, a C(═O)—R c  group, a C(═O)—OR c  group, a CH 2 (OR c ) group, a CH(OR c )CH 3  group wherein R c  is a C 1-4  alkyl group; R b  is a C 1-4  alkyl group, a C(═O)—R c  group wherein R c  is a C 1-4  alkyl group; or R a  and R b  are taken together and represent a C 2-6  alkanediyl group, R d  is a hydrogen atom or a CH(OR a )(OR b ) m  group wherein m, R a  and R b  have the same meaning as defined above. 
       
     
     
         2 . The process according to  claim 1 , wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8  and R 9  independently from each other, represent a hydrogen atom or a C 1-3  alkyl group. 
     
     
         3 . The process according to  claim 1 , wherein X is a group of formula a) or c). 
     
     
         4 . The process according to  claim 1 , wherein the compound of formula (I) is of formula (I″): 
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers or a mixture thereof, and wherein m, R a , R b , R 1  and R 2  have the same meaning as defined in  claim 1 ; 
       
       and said compound of formula (IIc) is of formula (IIc′) 
       
         
           
           
               
               
           
         
       
       in the form of any one of its stereoisomers or a mixture thereof, and wherein each R 1  and R 2  have the same meaning as defined in  claim 1 . 
     
     
         5 . The process according to  claim 1 , wherein R 1  is a C 1-4  alkyl group or a C 2-4  alkenyl group. 
     
     
         6 . The process according to  claim 1 , wherein R 1  is a methyl group. 
     
     
         7 . The process according to claim  11 , wherein R 2  is a hydrogen atom, a C 1-3  alkyl group or a C 2-3  alkenyl group. 
     
     
         8 . The process according to  claim 1 , wherein R 2  is a methyl group. 
     
     
         9 . The process according to  claim 1 , wherein R d  is a hydrogen atom and m is 1. 
     
     
         10 . The process according to  claim 1 , wherein the metathesis catalyst is a Ruthenium-based catalyst. 
     
     
         11 . The process according to  claim 1 , wherein the metathesis catalyst is selected from the group consisting of 1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)diiodo(2-((1-(methoxy(methyl)amino)-1-oxopropan-2-yl)oxy)benzylidene)ruthenium(II), (1,3-dimesitylimidazolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), Benzylidene-bis(tricyclohexylphosphine)dichlororuthenium, Dichloro[1,3-bis(2,6-isopropylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-Bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene)(2-i-propoxy-5-nitrobenzylidene) ruthenium(II) diiodide, 1,3-Bis(2,6-di-i-propylphenyl)imidazolidin-2-ylidene)(2-i-propoxy-5-nitrobenzylidene) ruthenium(II) dichloride, (1,3-Dimesitylimidazolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), Bis(1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)(3-phenyl-1H-inden-1-ylidene)ruthenium(II) dichloride, (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)dichloro(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), (1-(2,6-diethylphenyl)-3,5,5-trimethyl-3-phenylpyrrolidin-2-ylidene)diiodo(2-isopropoxy-5-nitrobenzylidene)ruthenium(II), Dichloro[1,3-bis(2-methylphenyl)-2-imidazolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), 1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride (resin supported), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(tricyclohexylphosphine)ruthenium(II), [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenolyl]-[3-phenyl-1H-inden-1-ylidene]ruthenium(II) chloride, Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][[5-[(dimethylamino)sulfonyl]-2-(1-methylethoxy-O)phenyl]methylene-C]ruthenium(II), Dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), [1,3-Bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]dichloro[(2-isopropoxy)(5-trifluoroacetamido)benzylidene]ruthenium(II), Dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)ruthenium(II), Dichloro[1-(2,4,6trimethylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), Dichloro[1-(2,6-diisopropylphenyl)-2,2,4-trimethyl-4-phenyl-5-pyrrolidinylidene](2-isopropoxyphenylmethylene)ruthenium(II), Dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]{[5-(2-ethoxy-2-oxoethanamido)]-2-isopropoxybenzylidene}ruthenium(II), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-pentafluorobenzoylamino)benzylidene]ruthenium(II), (1,3-Bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene)dichloro(2-((1-(methoxy(methyl)amino)-3-methyl-1-oxobutan-2-yl)oxy)benzylidene)ruthenium(II), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium(II), Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene][(2-isopropoxy)(5-trifluoroacetamido)benzylidene]ruthenium(II), Dichloro[1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene][(5-isobutoxycarbonylamino)-(2-isopropoxy)benzylidene]ruthenium(II) and Dichloro[1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene](3-phenyl-1H-inden-1-ylidene)(triphenylphosphine)ruthenium(II). 
     
     
         12 . The process according to  claim 1 , wherein the process further comprises the steps of converting compound of formula (I) to compound of formula (V); 
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers or a mixture thereof, and wherein X is a group of formula a) or b) having the same meaning as defined in  claim 1 . 
       
     
     
         13 . The process according to  claim 12 , wherein the preparation of compound of formula (V) comprises, when m is 1, a deprotection and hydrogenation step. 
     
     
         14 . The process according to  claim 12 , wherein the preparation of compound of formula (V) comprises, when m is 0, an isomerization and a deprotection step. 
     
     
         15 . A compound of formula (VIII): 
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers or a mixture thereof, and wherein X is a group of formula b) or d) 
       
       
         
           
           
               
               
           
         
         in the form of any one of its stereoisomers, and 
         wherein p is 0 when the dotted line is a carbon-carbon double bond and p is 1 when the dotted line is a carbon-carbon single bond; 
         each R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7 , independently from each other, represent a hydrogen atom, a C 1-6  alkyl group or a C 2-6  alkenyl group, each optionally substituted by a hydroxy or C 1-3  alkoxy group; or two groups among R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are taken together and form C 3-8  cycloalkyl or C 5-8  cycloalkenyl group, each optionally substituted by a hydroxy, C 1-3  alkyl or C 1-3  alkoxy group, and the others groups have the same meaning as defined above; 
         each R 8 , R 9  and R 10 , independently from each other, represent a hydrogen atom, a C 1-6  alkyl group or a C 2-6  alkenyl group, each optionally substituted by a hydroxy or C 1-3  alkoxy group; 
         or two groups among R 8 , R 9  and R 10  are taken together and form C 3-8  cycloalkyl or C 5-8  cycloalkenyl group, each optionally substituted by a hydroxy, C 1-3  alkyl or C 1-3  alkoxy group, and the other group has the same meaning as defined above; 
         n is 0 or 1; 
         Y is a —CH═CR 11 —, —CHR 12 —CHR 11 — or —CH 2 —C(OH)R 11 — group wherein R 11  is a hydrogen atom or a methyl or ethyl group and R 12  is a hydroxy or a acetate group; 
         Z is, when X is of formula d), a CHO group, a CH 2 OH group or a CH(OR a )(OR b ) m  group wherein m is 0 or 1, R a  is a C 1-4  alkyl group, a trimethyl silyl group, a C(═O)—R c  group, a C(═O)—OR c  group, a CH 2 (OR c ) group, a CH(OR c )CH 3  group wherein R c  is a C 1-4  alkyl group; R b  is a C 1-4  alkyl group, a C(═O)—R c  group wherein R c  is a C 1-4  alkyl group; or R a  and R b  are taken together and represent a C 2-6  alkanediyl group; or 
         Z is, when X is of formula b), a CH(OR a )(OR b ) group wherein R a  and R b , independently from each other, are a methyl group or a C 3-4  alkyl group, a C(═O)—R c  group wherein R c  is a C 1-4  alkyl group; or R a  and R b  are taken together and represent a C 3-6  alkanediyl group; and 
         provided that when X is a group of formula (d), then at least one group among R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  is a C 1-6  alkyl group or a C 2-6  alkenyl group, each optionally substituted by a hydroxy or C 1-3  alkoxy group; provided that when X is a group of formula (d) and six groups among R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are a hydrogen atom, then the group among R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  being not a hydrogen atom is not a methyl group; provided that when X is a group of formula (d) and R 2 , R 3 , R 4 , R 5 , R 6  and R 7  are a hydrogen atom then R 1  is not a prop-1-en-2-yl group; and provided that 3-(4-(tert-butyl)cyclohex-1-en-1-yl)acrylaldehyde, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)acrylaldehyde, 1-(tert-butyl)-4-(3,3-diethoxyprop-1-en-1-yl)benzene, 2-(4-(tert-butyl)styryl)-1,3-dioxolane, 3-(4-(tert-butyl)-1-hydroxycyclohexyl)allyl acetate, 3-(2-allyl-1-hydroxycyclohexyl)allyl acetate, 4-(tert-butyl)-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, 2-(4-isopropylstyryl)-1,3-dioxane, 2-(4-isopropylstyryl)-4-methyl-1,3-dioxolane, 3-(2-(buta-1,3-dien-1-yl)-1-hydroxycyclohexyl)acrylaldehyde, 3-(5,5-dimethylcyclohex-1-en-1-yl)acrylaldehyde, 3-((1S,5R)-6,6-dimethylbicyclo[3.1.1]hept-2-en-3-yl)acrylaldehyde, (1R,2S,5R)-1-(3-(tert-butoxy)prop-1-en-1-yl)-2-isopropyl-5-methylcyclohexan-1-ol, 2-allyl-1-(3-hydroxyprop-1-en-1-yl)cyclohexan-1-ol, (3,3-dimethoxyprop-1-en-1-yl)benzene, are excluded.